The pyridine/bis(pinacolate)diboron combination has been found to be able to initiate the iodoperfluoroalkylation of unactivated alkenes with perfluoroalkyl iodides. Theoretical calculations and control experiments indicate that the atom transfer radical addition mechanism is responsible for the formation of iodoperfluoroalkylation products. This metal-free and photo-free strategy is applicable to a wide range of perfluoroalkyl iodides and unactivated alkenes with good functional group tolerance. Further applications in iodoperfluoroalkylation of organic semiconductor-relevant or bioactive molecules demonstrate the synthetic potential of this method.